CN104878322A - Production technology of low-carbon weather-resistant steel - Google Patents
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Abstract
The invention discloses a production technology of low-carbon weather-resistant steel, belongs to the field of rolled steel preparation, and particularly relates to a method for controlling the surface quality of a rolled product of the low-carbon weather-resistant steel containing copper and stibium. Through design of liquid steel components, optimization of a continuous casting process and cooling control after a casting blank is discharged from a withdrawal and straightening machine, the surface quality of the casting blank is improved; enrichment and precipitation of low-melting point elements Cu and Sb on the crystal boundary in the casting blank cooling process are effectively inhibited; a hot charging process is adopted; the tapping interval is improved; the heating cost is reduced; the heating time in a furnace is shortened; the heating temperature is controlled; by virtue of high-temperature quick calcination, secondary enrichment of the low-melting point elements Cu and Sb along the austenite crystal boundary in the heating process is relieved; through the measures, the surface quality problem of the rolled product caused by corner cracks and crystal boundary cracks on the casting blank surface is greatly improved; and the barreling attrition rate of the rolled product is effectively reduced.
Description
Technical field
The invention belongs to field of steel preparation, particularly a kind of control method of surface quality when preparing cupric, antimony low-carbon (LC) weathering steel stocking.
Background technology
Cupric, antimony weathering steel are widely used in and are manufactured on the appliance arrangements such as economizer, air preheater, heat exchanger and the vaporizer of being on active service in high sulfur-containing smoke gas, for resisting sulfur-containing smoke gas dewing corrosion.Through long-term inspection, the weather-proof steel grade of cupric, antimony is generally considered domestic desirable " resistance to sulfuric acid low temperature corrosion " one of with steel, and its for hydrochloric acid (HCl), hydrofluoric acid (HF), caustic soda (NaOH), sodium-chlor (NaCl), have stronger corrosion resistance nature.In addition, in order to keep good welding property, carbon content is unsuitable too high.At present this weather-proof steel grade market requirement is good, and domesticly only has several Special Steel Enterprises at this weather-proof steel grade of production.
But this steel grade stocking surface very easily cracks.First, the carbon content of this steel grade is just in time in Peritectic Reaction district, and in a crystallizer, δ-Fe is converted into γ-Fe completely, and phase transformation volumetric shrinkage is large, and namely base shell linear shrinkage amount is large, and between such crystallizer wall and base shell, space is also large, thus very easily causes hot-fluid uneven; Two be the constituent contents such as Cu, Sb in this steel grade comparatively other steel grade obviously want high, in crystallisation process, segregation tendency is large, makes the embrittlement of grain boundaries of steel.Stocking crackle or cause for the continuously cast bloom original corner crack in surface and grain-boundary crack extend with rolling, or be that strand low melting point element such as Cu, Sb in heat-processed permeates enrichment along austenite grain boundary again, caused by the embrittlement of grain boundaries making steel.Carrying out pickling test discovery to this steel grade hot rolling material, there is obvious bark shape crackle and triangle crackle in this steel grade stocking surface usually.
The comparatively serious and general problem that distributes of this steel grade surface imperfection not only exists the stability of quality product to be affected largely, and add the surface finish workload of follow-up stocking, usual needs three road barreling is added some points and is ground process, average barreling wastage rate are up to about 4%, and this adds production fringe cost while reduction lumber recovery.Therefore, be necessary to take corresponding measure to improve the surface quality of this steel grade hot rolling material, reduce its barreling wastage rate.
Patent CN201210463981.4 and Chen R.Y. reports, by adding the nickel becoming 1:1 or content more at high proportion with copper content, the effect suppressing copper brittleness can be reached, but, adding of a large amount of Ni element, not only increase production cost, and too increase the tendency of this steel grade corrosion resistance nature deterioration; Liang Wen etc. then attempt adding a certain amount of rare earth at weather-proof steel grade, the add-on of Ni is reduced by Rare Earth Lanthanum, cerium, the fixed action of yttrium to low melting point element, but the application of rare earth in steel is still immature, rare earth price is more expensive on the one hand, RE-treated is improper on the other hand can increase being mingled with in steel on the contrary, worsen the performance of steel, the suitability of the method is limited and have the risk increasing molten steel inclusion; Chihiro Nagasaki etc. then serve the effect suppressing the copper in Copper Bearing Steel in crystal boundary enrichment by addition element boron, but this control method only rests on laboratory stage, and suitability is comparatively limited, is difficult to extensively promote to suitability for industrialized production.
It should be noted that equally, current patent and research mostly only control for the single production link in steel-making or the operation of rolling, and do not have to the whole process process control that steel-making strand, strand transhipment and rolling are become a useful person from Composition Design, and rarely has the impact of the antimony Surface Quality relating to high level.
Summary of the invention
Technical problem to be solved by this invention is: cupric, antimony weather-proof steel grade stocking surface easily occurs crackle, adds the surface finish workload of follow-up stocking, adds production fringe cost while reducing lumber recovery.
For solving this technical problem, the technical solution used in the present invention is: provide a kind of cupric, antimony low-carbon (LC) weathering steel, each composition of steel is calculated as by massfraction: C:0.07 ~ 0.012%, Si:0.30 ~ 0.50%, Mn:0.45 ~ 0.75%, P :≤0.025%, S :≤0.015%, Cr:0.80 ~ 1.00%, Cu:0.35 ~ 0.50%, Sb:0.08 ~ 0.15%, Ni:0.10 ~ 0.15%, Ti:0.015 ~ 0.020%, all the other are Fe.
Present invention also offers the preparation method of a kind of above-mentioned cupric, antimony low-carbon (LC) weathering steel, adopt the operational path of " EAF-CONVERTER electricity converter smelting+LF stove refining+VD vacuum-treat+CCM continuous casting process+heat send+hot rolling " to produce cupric, antimony weathering steel,
Wherein, in EAF-CONVERTER electricity converter steelmaking process, need to consider weathering steel use properties relevant resistance to atmospheric corrosion, intensity and toughness and welding property, concrete composition of smelting controlled as follows:
Steel scrap and molten iron require the low melting point element content < 0.010% such as Sn, As, reduce its impact on hot-short performance;
C content is 0.07 ~ 0.09%, reduces thermally denature drag while ensureing good welds performance, reduces the formation of crackle in the operation of rolling;
Cu improves the alloying element that steel corrosion resistance nature is main, the most generally use, Cu general control is more than 0.35%, but Cu element easily produces enrichment at crystal boundary, therefore its content is no more than 0.45%, the content of further raising Cu is not only little to weathering resistance contribution, very easily cause copper brittleness on the contrary, during actual smelting, Cu content controls by 0.35 ~ 0.40%;
The hardness being added in raising steel of Sb element and the corrosion proof fragility simultaneously too increasing steel, Sb content controls by 0.08 ~ 0.10%;
Ni can form alloy with low melting point elements such as Cu, the Sb in molten steel and effectively suppress its enrichment at crystal boundary to be separated out, usual Ni content just can play the effect alleviating copper brittleness more than 0.10%, but Ni element is noble metal, therefore its target content span of control is 0.10 ~ 0.15%, to suppress the red brittleness of steel and to take into account the economy of smelting cost;
Si, Mn, Cr control in 0.35 ~ 0.45%, 0.50 ~ 0.60%, 0.85 ~ 0.95% scope respectively to realize good toughness and tenacity and to act on corrosion proof supplement;
Add ferrotianium makes finished product Ti content be 0.015 ~ 0.020% simultaneously, makes up the low undercapacity caused of carbon further;
P, S then control respectively in≤0.025% and≤0.015% scope;
On the basis that mentioned component controls, EAF-CONVERTER electricity converter smelting, the refining of LF stove, VD vacuum-treat adopt technique of the prior art to carry out.
Optimized Process of CC and control: Cross Section of CC Billet is of a size of 220mm × 260mm, continuous casting superheating temperature is stabilized between 15 ~ 25 DEG C, this is while the higher pulling rate of follow-up employing establishes Process ba-sis, is also conducive to reducing the segregation enrichments of low melting point element in casting cycle such as Cu, Sb; Strict control one cold water flow: 100-105m
3/ h, an inlet water temperature: 30 ± 3 DEG C, the cold water temperature difference a: 7-9 DEG C, to ensure the weak cold and heat transfer homogeneity of strand in crystallizer, use peritectic steel mould flux simultaneously, strengthen the lubrication between strand and crystallization wall, prevent casting billet surface from occurring depression and crackle; Pulling speed of continuous casting is 0.95 ± 0.5m/min, suitably can regulate according to molten steel temperature and rhythm of production, specific water is set as 0.25L/kg, guarantees that casting billet surface and bight temperature are within the scope of 950 ~ 980 DEG C before entering withdrawal straightening machine, thus reduces the occurrence probability of straightening cracks; Casting blank heat-insulating cover after cancellation withdrawal straightening machine on ejection roller way, improve the rate of cooling of strand in ejection, reduce low melting point element in this process, the particularly precipitation rate of Sb, thus alleviate its enrichment at blank surface, simultaneously by adjusting blank roller way rotating speed, avoiding strand undercooling in ejection, guaranteeing that strand entrucking temperature controls within the scope of 600 ~ 650 DEG C.
Heat send control: by adopting the hot conveying vehicle Special heat preservation cover with thermal insulation layer, temperature drop heat passed through in journey controls within 50 DEG C, simultaneously according to the production capacity production plan of production specification and different production line, to improve the matching of steel-making and Rolling production rhythm, reduce the waiting time of strand outside process furnace, realize strand charging temperature 550 ~ 600 DEG C.
Hot rolling technology controls: in process furnace, maximum heating temperature is increased to 1250 DEG C, strand is avoided to stop for a long time in the strongest wetting property of liquid Cu phase of 1100 ~ 1200 DEG C and perviousness temperature range, when Heating temperature is at 1100 ~ 1200 DEG C, the wetting property of copper is the strongest, therefore, the hand down infiltration of austenite grain boundary of the liquid copper that enrichment is formed at such a temperature is the easiest, also more easily produces copper brittleness; Continue to raise with Heating temperature, cause weakening and the enhancing of diffusibility of the wettability of copper, measuring copper and the infiltration along crystal boundary weaken on the contrary, and when being heated to 1250 DEG C, liquid copper disappears mutually substantially, and copper brittleness effect weakens,
Produce steel grade before and after this steel grade arranges heat to send steel grade simultaneously as far as possible, improve tapping interval to 80 ~ 100 second, and strand is compressed to 105 ~ 125 minutes the heat-up time in process furnace, air-fuel ratio 0.5 ~ 0.6 is adopted in process furnace, control week reduction or neutral atmosphere, alleviate the secondary enrichment of the low melting point elements such as Cu, Sb in heat-processed along austenite grain boundary further; Strand start rolling temperature controls within the scope of 1080 ~ 1130 DEG C.
Beneficial effect of the present invention is: the present invention play Ni inhibiting to copper brittleness while, greatly reduce the add-on of Ni, thus reduce production cost and Ni to the degradation effects of this steel grade erosion resistance; Go out the cooling after withdrawal straightening machine by molten steel component design, Optimized Process of CC and strand to control, improve cc billet surface quality, and effectively inhibit low melting point element Cu, Sb in slab cooling process to separate out in the enrichment of crystal boundary; Heat is adopted to send technique and improve tapping interval, while reducing heating cost, reduce heat-up time in stove, control Heating temperature, adopt high temperature rapid firing, avoid the temperature province that Cu, Sb seepage force is the strongest as far as possible, thus to alleviate in heat-processed the low melting point element such as Cu, Sb along the secondary enrichment of austenite grain boundary; Substantially improve the stocking surface quality problems because casting billet surface corner crack and grain-boundary crack cause by above-mentioned measure, effectively reduce stocking barreling wastage rate.
Present invention covers produce weathering steel time steel-making and rolling process in all key links, while each control flow compatibility of enhancing, make this patent have more careful property for the control of surface quality in actual production process, and other weather-proof steel grade is had equally with reference to suitability.
Embodiment
Embodiment 1
Adopt EAF-CONVERTER electricity converter smelting → LF stove refining → VD vacuum-treat → CCM continuous casting → heat give → operational path of hot rolling produces cupric, antimony low-carbon (LC) weathering steel.
Smelt finished product composition to control: C:0.07%, Si:0.39%, Mn:0.52%, Cr:0.95%, Cu:0.37%, Sb:0.09%, Ni:0.12%, Ti:0.017%, P:0.020%, S:0.003%, all the other are Fe.
Continuous casting superheating temperature 22 DEG C, a cold water flow 102m
3/ h; inflow temperature 31 DEG C, a cold water temperature difference 7.6 DEG C, two cold specific water 0.25L/kg; pulling rate is 0.95m/min; use peritectic steel mould flux, strand enters withdrawal straightening machine temperature 952 ~ 978 DEG C, the casting blank heat-insulating cover after cancellation withdrawal straightening machine on ejection roller way; improve the rate of cooling of strand in ejection; simultaneously by adjusting blank roller way rotating speed, avoid strand undercooling and make strand temperature too low in ejection, strand entrucking temperature 624 ~ 637 DEG C.
This batch of production specification is Φ 80mm, adopt the special hot conveying vehicle of band heat insulation layer structure stay-warm case hot base to be delivered to six and roll three lines productions, strand charging temperature 569 ~ 589 DEG C, maximum heating temperature (i.e. target temperature) in process furnace is 1248 DEG C, and process furnace temperature rise rate is 15 DEG C/min, 115 minutes total heat-up times, in process furnace, air-fuel ratio is 0.52, strand start rolling temperature 1105 ~ 1123 DEG C, finishing temperature 952 ~ 958 DEG C, average tapping interval is 84 seconds.
By above-mentioned implementation method, gained cupric, antimony low-carbon (LC) weathering steel hot rolling material add some points mill by one barreling can by surface crack removing to the greatest extent, and barreling wastage rate are 1.96%.
Embodiment 2:
Adopt EAF-CONVERTER electricity converter smelting → LF stove refining → VD vacuum-treat → CCM continuous casting → heat give → operational path of hot rolling produces cupric, antimony low-carbon (LC) weathering steel.
Smelt finished product composition to control: C:0.07%, Si:0.41%, Mn:0.51%, Cr:0.93%, Cu:0.36%, Sb:0.08%, Ni:0.13%, Ti:0.015%, P:0.018%, S:0.002%, all the other are Fe.
Continuous casting superheating temperature 24 DEG C, a cold water flow 100m
3/ h; inflow temperature 29 DEG C, a cold water temperature difference 8.1 DEG C, two cold specific water 0.25L/kg; pulling rate is 0.98m/min; use peritectic steel mould flux, strand enters withdrawal straightening machine temperature 961 ~ 982 DEG C, the casting blank heat-insulating cover after cancellation withdrawal straightening machine on ejection roller way; improve the rate of cooling of strand in ejection; simultaneously by adjusting blank roller way rotating speed, avoid strand undercooling and make strand temperature too low in ejection, strand entrucking temperature 628 ~ 643 DEG C.
This batch of production specification is Φ 50mm, adopt the special hot conveying vehicle of band heat insulation layer structure stay-warm case hot base to be delivered to six and roll two wires production, strand charging temperature 573 ~ 596 DEG C, maximum heating temperature (i.e. target temperature) in process furnace is 1252 DEG C, and process furnace temperature rise rate is 15 DEG C/min, 109 minutes total heat-up times, in process furnace, air-fuel ratio is 0.53, strand start rolling temperature 1112 ~ 1127 DEG C, finishing temperature 948 ~ 957 DEG C, average tapping interval is 92 seconds.
By above-mentioned implementation method, surface crack can be removed to the greatest extent by one barreling by gained cupric, antimony low-carbon (LC) weathering steel hot rolling material, and barreling wastage rate are 1.85%.
Embodiment 3:
Adopt EAF-CONVERTER electricity converter smelting → LF stove refining → VD vacuum-treat → CCM continuous casting → heat give → operational path of hot rolling produces cupric, antimony low-carbon (LC) weathering steel.
Smelt finished product composition to control: C:0.08%, Si:0.40%, Mn:0.54%, Cr:0.92%, Cu:0.39%, Sb:0.09%, Ni:0.14%, Ti:0.017%, P:0.021%, S:0.002%, all the other are Fe.
Continuous casting superheating temperature 20 DEG C, a cold water flow 105m
3/ h; inflow temperature 32 DEG C, a cold water temperature difference 7.7 DEG C, two cold specific water 0.25L/kg; pulling rate is 0.92m/min; use peritectic steel mould flux, strand enters withdrawal straightening machine temperature 951 ~ 971 DEG C, the casting blank heat-insulating cover after cancellation withdrawal straightening machine on ejection roller way; improve the rate of cooling of strand in ejection; simultaneously by adjusting blank roller way rotating speed, avoid strand undercooling and make strand temperature too low in ejection, strand entrucking temperature 611 ~ 632 DEG C.
This batch of production specification is Φ 65mm, adopt the special hot conveying vehicle of band heat insulation layer structure stay-warm case hot base to be delivered to six and roll three lines productions, strand charging temperature 558 ~ 576 DEG C, maximum heating temperature (i.e. target temperature) in process furnace is 1250 DEG C, and process furnace temperature rise rate is 15 DEG C/min, 112 minutes total heat-up times, in process furnace, air-fuel ratio is 0.50, strand start rolling temperature 1098 ~ 1112 DEG C, finishing temperature 951 ~ 959 DEG C, average tapping interval is 89 seconds.
By above-mentioned implementation method, surface crack can be removed to the greatest extent by one barreling by gained cupric, antimony low-carbon (LC) weathering steel hot rolling material, and barreling wastage rate are 1.76%.
The carbon equivalent of the cupric of the present embodiment gained, the mechanical property of antimony low-carbon (LC) weathering steel, corrosion resistance to sulfuric acid and reflection welding property is as shown in table 1:
Table 1 embodiment 3 produces the mechanical property of steel grade, corrosion resistance nature and carbon equivalent
* the condition determination of erosion resistance is: be 50%H the concentration of 70 DEG C
2sO
424h is soaked in solution
As shown in Table 1, obtained under the present embodiment condition cupric, the mechanical property of antimony low-carbon (LC) weathering steel, corrosion resistance nature meet the requirement of concerned countries standard completely.Simultaneously, carbon equivalent Ce=0.285<0.4 is calculated according to carbon equivalent calculation formula Ce=C+Mn/6+ (Cr+Mo+V)/5+ (Ni+Cu)/15 that International Institude of Welding IIW recommends, this shows that the welding property of steel is good, does not need to carry out preheating and postweld heat treatment.
Comparative example 1
Adopt EAF-CONVERTER electricity converter smelting → LF stove refining → VD vacuum-treat → CCM continuous casting → heat give → operational path of hot rolling produces cupric, antimony low-carbon (LC) weathering steel.
Smelt finished product composition to control: C:0.07%, Si:0.40%, Mn:0.52%, Cr:0.95%, Cu:0.37%, Sb:0.08%, Ni:0.12%, Ti:0.017%, P:0.020%, S:0.003%, all the other are Fe.
Continuous casting superheating temperature 22 DEG C, a cold water flow 102m
3/ h; inflow temperature 31 DEG C, a cold water temperature difference 7.6 DEG C, two cold specific water 0.25L/kg; pulling rate is 0.95m/min; use peritectic steel mould flux, strand enters withdrawal straightening machine temperature 952 ~ 978 DEG C, the casting blank heat-insulating cover after cancellation withdrawal straightening machine on ejection roller way; improve the rate of cooling of strand in ejection; simultaneously by adjusting blank roller way rotating speed, avoid strand undercooling and make strand temperature too low in ejection, strand entrucking temperature 624 ~ 637 DEG C.
This batch of production specification is Φ 80mm, adopt the special hot conveying vehicle of band heat insulation layer structure stay-warm case hot base to be delivered to six and roll three lines productions, strand charging temperature 569 ~ 589 DEG C, maximum heating temperature (i.e. target temperature) in process furnace is 1150 DEG C, and process furnace temperature rise rate is 15 DEG C/min, 160 minutes total heat-up times, in process furnace, air-fuel ratio is 0.52, strand start rolling temperature 1055 ~ 1113 DEG C, finishing temperature 952 ~ 958 DEG C, average tapping interval is 102 seconds.
By above-mentioned implementation method, surface crack cannot be removed to the greatest extent by one barreling mill of adding some points by gained cupric, antimony low-carbon (LC) weathering steel hot rolling material, and just realized surface crack eliminated by 3 road barreling mill of adding some points, barreling wastage rate are 3.89%.
The carbon equivalent of the cupric of comparative example 1 gained, the mechanical property of antimony low-carbon (LC) weathering steel, corrosion resistance to sulfuric acid and reflection welding property is as shown in table 2:
Table 2
* the condition determination of erosion resistance is: be 50%H the concentration of 70 DEG C
2sO
424h is soaked in solution.
Claims (8)
1. a low-carbon (LC) weathering steel, is characterized in that: each composition of described weathering steel is calculated as by massfraction, C 0.07 ~ 0.012%, Si 0.30 ~ 0.50%, Mn 0.45 ~ 0.75%, P≤0.025%, S≤0.015%, Cr 0.80 ~ 1.00%, Cu0.35 ~ 0.50%, Sb 0.08 ~ 0.15%, Ni 0.10 ~ 0.15%, Ti 0.015 ~ 0.020%, all the other are Fe.
2. a preparation method for low-carbon (LC) weathering steel, is characterized in that: described preparation method is,
The operational path of " EAF-CONVERTER electricity converter smelting+LF stove refining+VD vacuum-treat+CCM continuous casting process+heat send+hot rolling " is adopted to produce cupric, antimony weathering steel,
Wherein, in described EAF-CONVERTER electricity converter steelmaking process, calculate by massfraction, control that C content in steel scrap and molten iron is 0.07 ~ 0.09%, Cu content is 0.35 ~ 0.40%, Sb content is 0.08 ~ 0.10%, Ni content is 0.10 ~ 0.15%, Si content is 0.35 ~ 0.45%, Mn content is 0.50 ~ 0.60%, Cr content is 0.85 ~ 0.95%, P content≤0.025%, S content≤0.015%;
In described CCM continuous casting process, Cross Section of CC Billet is of a size of 220mm × 260mm, and continuous casting superheating temperature is stabilized between 15 ~ 25 DEG C, and controlling a cold water flow is 100-105m
3/ h, an inlet water temperature is 30 ± 3 DEG C, and a cold water temperature difference is 7-9 DEG C, controls before entering withdrawal straightening machine that casting billet surface and bight temperature are within the scope of 950 ~ 980 DEG C, and strand entrucking temperature controls within the scope of 600 ~ 650 DEG C;
In described hot rolling technology, strand charging temperature is 550 ~ 600 DEG C, and the temperature rise rate of process furnace is 10 ~ 15 DEG C/min, and in process furnace, maximum heating temperature is 1250 DEG C, and the heat-up time of strand in process furnace is 105 ~ 125 minutes.
3. the preparation method of low-carbon (LC) weathering steel as claimed in claim 2, it is characterized in that: in described CCM continuous casting process, control pulling speed of continuous casting is 0.95 ± 0.5m/min, and specific water is 0.25L/kg.
4. the preparation method of low-carbon (LC) weathering steel as claimed in claim 2, is characterized in that: described heat passes through in journey, is controlled within 50 DEG C by temperature drop.
5. the preparation method of low-carbon (LC) weathering steel as claimed in claim 4, is characterized in that: described heat passes through in journey, adopts the hot conveying vehicle Special heat preservation cover with thermal insulation layer.
6. the preparation method of low-carbon (LC) weathering steel as claimed in claim 2, is characterized in that: in described course of hot rolling, and controlling tapping interval is 80 ~ 100 seconds.
7. the preparation method of low-carbon (LC) weathering steel as claimed in claim 2, it is characterized in that: in described course of hot rolling, in process furnace, air-fuel ratio is 0.5 ~ 0.6.
8. the preparation method of low-carbon (LC) weathering steel as claimed in claim 2, it is characterized in that: in described course of hot rolling, strand start rolling temperature controls at 1080 ~ 1130 DEG C.
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Effective date of registration: 20190603 Address after: 213000 No. 1 Zhongwu Avenue, Changzhou City, Jiangsu Province Co-patentee after: Changzhou Bangyi Iron and Steel Co., Ltd. Patentee after: Zhongtian Iron Steel Group Co.,Ltd. Address before: 213011 beside 312 National Road, Yinshu Village, Yaoguan Town, Wujin District, Changzhou City, Jiangsu Province Patentee before: Zhongtian Iron Steel Group Co.,Ltd. |